Oxidation of phosphido-bridged complexes of molybdenum and tungsten. Isolation of [cyclic] [trans-(HPh2P)(OC)3M(.mu.-PPh2)2M(CO)3(PPh2H)][PF6]

Keiter, Richard L.; Keiter, Ellen A.; Rust, Merle S.; Miller, David R.; Sherman, Edward; Cooper, D. E.

doi:10.1021/om00037a084

Cited by 11 publications

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“…There are precedents of this sort of behavior in diphenylphosphide-bridged complexes. For example, a fully reversible oxidation wave was observed for the complexes [M 2 (μ-PPh 2 ) 2 (CO) 6 (PPh 2 H) 2 ] (M = Mo, W), despite the reorganization of the carbonyl ligands (from mer to fac ) occurring after one-electron oxidation 2c, in agreement with the IR data discussed above.…”

Section: Resultssupporting

confidence: 85%

Chemical and Electrochemical Oxidation of Diphenylphosphide-Bridged Hydrides [M₂(η⁵-C₅H₅)₂(μ-H)(μ-PPh₂)(CO)₄] and Anions [M₂(η⁵-C₅H₅)₂(μ-PPh₂)(CO)₄]^-(M = Mo, W)

et al. 2005

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Reaction of the hydride complexes [M 2 Cp 2 (µ-H)(µ-PPh 2 )(CO) 4 ] (M ) Mo, W; Cp ) η 5 -C 5 H 5 ) with [FeCp 2 ]BF 4 proceeds in a 1:2 ratio to give the unsaturated tetracarbonyl salts [M 2 Cp 2 -(µ-PPh 2 )(CO) 4 ]BF 4 , which spontaneously (M ) Mo) or in the presence of CO (M ) W) transform into the corresponding electron-precise pentacarbonyls [M 2 Cp 2 (µ-PPh 2 )(µ-CO)-(CO) 4 ]BF 4 . In contrast, reaction of the above hydride complexes with [FeCp 2 ](BAr′ 4 ) (Ar′ ) 3,5-C 6 H 3 (CF 3 ) 2 ) proceeds in a 1:1 ratio to give the paramagnetic salts [M 2 Cp 2 (µ-H)(µ-PPh 2 )-(CO) 4 ](BAr′ 4 ). No further reaction takes place with [FeCp 2 ](BAr′ 4 ) unless a proton acceptor such as water or tetrahydrofuran is present, in which case the corresponding salts [M 2 Cp 2 -(µ-PPh 2 )(CO) 4 ](BAr′ 4 ) or [M 2 Cp 2 (µ-PPh 2 )(µ-CO)(CO) 4 ](BAr′ 4 ) are rapidly formed. Reactions of the anions [M 2 Cp 2 (µ-PPh 2 )(CO) 4 ] -(as (H-DBU) + salts, DBU ) 1,8-diazabicyclo[5.4.0]undec-7-ene) with [FeCp 2 ]BF 4 proceed stepwise to give first the 33-electron radicals [M 2 Cp 2 (µ-PPh 2 )(CO) 4 ], which can be isolated as very air-sensitive green solids, and then the unsaturated salts [M 2 Cp 2 (µ-PPh 2 )(CO) 4 ]BF 4 , which are identical to those formed from the neutral hydrides. The structure and dynamic behavior of the new compounds are analyzed on the basis of solution IR, 1 H, 31 P, and 13 C NMR or ESR spectroscopic data. In addition, the redox and other chemical transformations connecting all the new compounds are discussed on the basis of the synthetic and structural data, as well as cyclic voltammetry measurements carried out in dichloromethane on the neutral hydrides [M 2 Cp 2 (µ-H)(µ-PPh 2 )-(CO) 4 ] and the anions [M 2 Cp 2 (µ-PPh 2 )(CO) 4 ] -(as [N(PPh 3 ) 2 ] + salts).

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Section: Resultssupporting

confidence: 85%

Chemical and Electrochemical Oxidation of Diphenylphosphide-Bridged Hydrides [M₂(η⁵-C₅H₅)₂(μ-H)(μ-PPh₂)(CO)₄] and Anions [M₂(η⁵-C₅H₅)₂(μ-PPh₂)(CO)₄]^-(M = Mo, W)

et al. 2005

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“…The latter turns to yellow in a few minutes at that temperature, or instantaneously if warmed, and the IR spectrum shows then the C−O bands of the corresponding mononuclear cations [MCp(CO) 2 (dppm)] + ( B ). We note here that the 33-electron radical [W 2 ( μ -PPh 2 ) 2 (CO) 6 (PPh 2 H) 2 ] + also exhibits a green color …”

Section: Resultsmentioning

confidence: 78%

“…b Recorded at 121.50 MHz and 291 K in CD 2 Cl 2 solution, unless otherwise stated; δ in ppm relative to external 85% aqueous H 3 PO 4 ; J in hertz. c PP and PW coupling constants are obtained from the 183 W “satellite” lines (see ref b). d In Nujol mull.…”

Section: Resultsmentioning

confidence: 99%

“…Typical secondary processes are solvent coordination or ligand rearrangements. , The latter processes can be sometimes avoided by the use of bridging ligands which increase the stability of the unsaturated cation. This is the case, for example, of the 33-electron dimers [W 2 ( μ -PPh 2 ) 2 (CO) 6 (PPh 2 H) 2 ] + and [Mo 2 ( μ -C 5 H 4 PPh 2 ) 2 (CO) 4 ] + , where the diphenylphosphido or cyclopentadienyl(diphenyl)phosphine bridging ligands no doubt play a determinant stabilizing role. The latter complex is prepared through oxidation of neutral dimer [Mo 2 ( μ -C 5 H 4 PPh 2 ) 2 (CO) 4 ], but removal of two electrons leads to decomposition.…”

Section: Introductionmentioning

confidence: 99%

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Chemistry of Highly Electrophilic Binuclear Cations. 1. Oxidation Reactions of [M₂(η⁵-C₅H₅)₂(CO)₄(μ-Ph₂PCH₂PPh₂)] (M = Mo, W) with [FeCp₂]X (X = BF₄, PF₆)

Alvarez¹,

García²,

Garcı́a³

et al. 1999

Organometallics

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Oxidation of the title compounds with 2 equiv of [FeCp2]BF4 in dichloromethane leads to the tetracarbonylic fluoro complexes [M2Cp2(μ-F)(CO)4(μ-dppm)]BF4 in high yields (dppm = Ph2PCH2PPh2). By contrast, the analogous reaction with [FeCp2]PF6 gives the tricarbonylic fluoro derivatives [M2Cp2(μ-F)(μ-CO)(CO)2(μ-dppm)]PF6. Separate experiments revealed that the latter cations cannot be obtained through decarbonylation of the former fluoro complexes. By carrying out the [FeCp2]PF6 oxidations in the presence of halide ions X- (X = Cl, Br, I), the corresponding halo derivatives [M2Cp2(μ-X)(μ-CO)(CO)2(μ-dppm)]PF6 are formed in good yields. All above species are derived from the unsaturated dications [M2Cp2(μ-CO)2(CO)2(μ-dppm)]2+, which are the initial products of the removal of two electrons from the title compounds. Despite its high reactivity, the tungsten dication can be isolated as a solid, thanks to its low solubility in dichloromethane, and has been shown to react with other donor molecules such as acetate ions or methanol, to give tricarbonylic derivatives [W2Cp2(μ-Y)(μ-CO)(CO)2(μ-dppm)]PF6 (Y = O2CMe, OMe), which display structures comparable to those of the corresponding halogeno complexes. The structure of both tungsten fluoro complexes has been determined by X-ray diffraction methods, that on the tetracarbonylic compound revealing the presence of a weak H-bonding interaction between the BF4 - counterion and a methylenic hydrogen in the diphosphine ligand. The reaction pathways likely operative in the oxidation of the title compounds are analyzed in light of the experimental findings and the critical role played by the BF4 - or PF6 - counterions.

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“…In addition to these neutral complexes, some anionic derivatives have been reported, for example, [{(CO) 4 M} 2 (μ-PR 2 ) 2 ] 2– (M = Cr, Mo, W; R = Me, Ph) − and [{(CO) 3 Fe} 2 (μ-PPh 2 ) 2 ] 2– . , …”

Section: Introductionmentioning

confidence: 99%

Transition-Metal Complexes Containing Parent Phosphine or Phosphinyl Ligands and Their Use as Precursors for Phosphide Nanoparticles

et al. 2014

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P-H functional transition-metal complexes were synthesized without using hazardous PH3 gas in good yields by photolysis of the transition-metal carbonyl complexes M(CO)(6-x) (M = Cr, W, Fe; x = 0, 1) in tetrahydrofuran followed by reaction with P2(SiMe3)4 and subsequent methanolysis to give the bridging complexes [(CO)(x)M(μ-PH2)]2 (M = Fe, x = 3 (1), M = Cr, x = 4 (2a), M = W, x = 4 (2b)). The photolysis of [(CO)4M(μ-PH2)]2 (M = Cr (2a), M = W (2b)) with P(SiMe3)3 was applied followed by methanolysis to synthesize the PH2 bridging transition-metal binuclear complexes with terminal PH3 groups. The products [(CO)4M(μ-PH2)2M(CO)3(PH3)] (M = Cr (3a), M = W (3b)) and [(CO)4W(μ-PH2)2W(CO)2(PH3)2] (4b) were isolated in moderate yield. Another synthetic approach to this type of compounds is the direct photolysis of the complexes [(CO)3M(PH3)3] (M = Cr (5a), M = W (5b)). The products were comprehensively characterized by (31)P NMR and IR spectroscopy as well as by X-ray structural analysis. Additionally, the relevancy of 2a as single source precursor for the synthesis of stoichiometry-controlled CrP nanoparticles has been demonstrated.

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Oxidation of phosphido-bridged complexes of molybdenum and tungsten. Isolation of [cyclic] [trans-(HPh2P)(OC)3M(.mu.-PPh2)2M(CO)3(PPh2H)][PF6]

Cited by 11 publications

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Chemical and Electrochemical Oxidation of Diphenylphosphide-Bridged Hydrides [M₂(η⁵-C₅H₅)₂(μ-H)(μ-PPh₂)(CO)₄] and Anions [M₂(η⁵-C₅H₅)₂(μ-PPh₂)(CO)₄]^-(M = Mo, W)

Chemical and Electrochemical Oxidation of Diphenylphosphide-Bridged Hydrides [M₂(η⁵-C₅H₅)₂(μ-H)(μ-PPh₂)(CO)₄] and Anions [M₂(η⁵-C₅H₅)₂(μ-PPh₂)(CO)₄]^-(M = Mo, W)

Chemistry of Highly Electrophilic Binuclear Cations. 1. Oxidation Reactions of [M₂(η⁵-C₅H₅)₂(CO)₄(μ-Ph₂PCH₂PPh₂)] (M = Mo, W) with [FeCp₂]X (X = BF₄, PF₆)

Transition-Metal Complexes Containing Parent Phosphine or Phosphinyl Ligands and Their Use as Precursors for Phosphide Nanoparticles

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Oxidation of phosphido-bridged complexes of molybdenum and tungsten. Isolation of [cyclic] [trans-(HPh2P)(OC)3M(.mu.-PPh2)2M(CO)3(PPh2H)][PF6]

Cited by 11 publications

References 0 publications

Chemical and Electrochemical Oxidation of Diphenylphosphide-Bridged Hydrides [M2(η5-C5H5)2(μ-H)(μ-PPh2)(CO)4] and Anions [M2(η5-C5H5)2(μ-PPh2)(CO)4]-(M = Mo, W)

Chemical and Electrochemical Oxidation of Diphenylphosphide-Bridged Hydrides [M2(η5-C5H5)2(μ-H)(μ-PPh2)(CO)4] and Anions [M2(η5-C5H5)2(μ-PPh2)(CO)4]-(M = Mo, W)

Chemistry of Highly Electrophilic Binuclear Cations. 1. Oxidation Reactions of [M2(η5-C5H5)2(CO)4(μ-Ph2PCH2PPh2)] (M = Mo, W) with [FeCp2]X (X = BF4, PF6)

Transition-Metal Complexes Containing Parent Phosphine or Phosphinyl Ligands and Their Use as Precursors for Phosphide Nanoparticles

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Chemical and Electrochemical Oxidation of Diphenylphosphide-Bridged Hydrides [M₂(η⁵-C₅H₅)₂(μ-H)(μ-PPh₂)(CO)₄] and Anions [M₂(η⁵-C₅H₅)₂(μ-PPh₂)(CO)₄]^-(M = Mo, W)

Chemical and Electrochemical Oxidation of Diphenylphosphide-Bridged Hydrides [M₂(η⁵-C₅H₅)₂(μ-H)(μ-PPh₂)(CO)₄] and Anions [M₂(η⁵-C₅H₅)₂(μ-PPh₂)(CO)₄]^-(M = Mo, W)

Chemistry of Highly Electrophilic Binuclear Cations. 1. Oxidation Reactions of [M₂(η⁵-C₅H₅)₂(CO)₄(μ-Ph₂PCH₂PPh₂)] (M = Mo, W) with [FeCp₂]X (X = BF₄, PF₆)